Polycarbonate resin, molded article, optical member, and lens

ABSTRACT

Disclosed is a polycarbonate resin having a constitutional unit represented by Formula (1). The resin provides a molded article having a sufficiently low Abbe number and having high abnormal dispersibility may be molded. Y 1  and Y 2  are an oxygen, sulfur, nitrogen or carbon atom; Z is an atomic group for forming a 5- to 7-membered ring; R 5  to R 8  represent a substituent; and Ar 11  and Ar 12  represent an aryl or heteroaryl group.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2017/006297, filed on Feb. 21, 2017, which claims priority under35 U.S.C. Section 119(a) to Japanese Patent Application No. 2016-032184filed on Feb. 23, 2016. Each of the above applications is herebyexpressly incorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a polycarbonate resin, a moldedarticle, an optical member, and a lens.

2. Description of the Related Art

In the related art, a glass material has been used in an optical memberof an image pick-up module of a camera, a video camera, acamera-equipped cellular phone, a videophone, a camera-equippedintercom, or the like. Since a glass material has various opticalproperties and has excellent environmental resistance, the glassmaterial has been preferably used but has disadvantages in thatreduction in weight and size is not easy, and workability andproductivity are poor. On the other hand, a resin cured product may bemass-produced and may have excellent workability, and thus the resincured product has been used for various optical members in recent years.

An optical member using a resin cured product has been studied toexhibit various optical properties and to improve durability by using acured product of a resin including a constitutional unit having aspecific structure.

For example, in JP2010-254806A, JP2013-64117A, and JP4010810B, resinseach including a constitutional unit having a fluorene skeleton andresin cured products are disclosed. In JP2010-254806A, a polycarbonateresin including 9,9-bis(4-hydroxy-3-methylphenyl) fluorene andbis(4-hydroxy-3-methylphenyl) sulfide is disclosed. In JP2013-64117A, apolyester resin using a dicarboxylic acid component including amonocyclic aromatic dicarboxylic acid component and a dicarboxylic acidcomponent having a fluorene skeleton and a diol component including acompound having a 9,9-bis(hydroxy (poly) alkoxyaryl) fluorene skeletonas polymerization components is disclosed. In JP4010810B, apolycarbonate resin having a fluorene skeleton, which is a resinincluding a constitutional unit having negative refractive indexanisotropy and a constitutional unit having positive refractive indexanisotropy is disclosed.

SUMMARY OF THE INVENTION

In recent years, along with miniaturization of image pick-up modules,miniaturizing optical members used in image pick-up modules has beenrequired. As the optical member becomes miniaturized, chromaticaberration becomes problematic, and thus correcting the chromaticaberration by reducing the Abbe number has been studied. However, thepresent inventors have studied the use of the above-described resinincluding a constitutional unit having a fluorene skeleton as an opticalmember, and have clearly found that, in a resin cured product in therelated art, the Abbe number is not sufficiently reduced. With respectto the resin cured product in the related art, it was clearly found thatabnormal dispersibility tends to be low.

Therefore, in order to solve the problems in the related art, thepresent inventors have conducted research for the purpose of providing aresin that is able to mold a resin cured product having a sufficientlylow Abbe number and a high abnormal dispersibility.

As a result of intensive studies in order to solve the above problems,the present inventors have found that, in a case where a polycarbonateresin including a constitutional unit having a specific structure isused, a resin cured product having a sufficiently low Abbe number(hereinafter, also referred to as a molded article) and a molded articlehaving high abnormal dispersibility may be obtained.

Specifically, the present invention has the following configuration.

[1] A polycarbonate resin having a constitutional unit represented byFormula (1);

in Formula (1), Y¹ and Y² are each independently an oxygen atom, asulfur atom, a nitrogen atom, or a carbon atom, and at least one of Y¹or Y² is an oxygen atom, a sulfur atom, or a nitrogen atom; Z is anatomic group for forming a 5- to 7-membered ring together with Y¹—C═C—Y²and represents an atomic group including at least one selected from acarbon atom and a heteroatom;

R⁵ to R⁸ each independently represent a substituent;

a to d are each independently 0 or more and represent an integer of themaximum number or less by which each ring is substitutable;

Ar¹¹ and Ar¹² each independently represent an aryl group including abenzene ring surrounded by a broken line or a heteroaryl group includinga benzene ring surrounded by a broken line as one of fused rings;

L¹ and L² each independently represent an alkylene group having 2 to 8carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, anarylene group having 6 to 20 carbon atoms, or a heteroarylene grouphaving 6 to 20 carbon atoms;

X¹ and X² each independently represent an oxygen atom or a sulfur atom;

n1 and n2 each independently represent an integer of 0 to 10; and

in a case where Ar¹¹ and Ar¹² are each independently an aromatic fusedring group including a benzene ring surrounded by a broken line, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or substitutedat a fused ring other than the benzene ring surrounded by a broken line.

[2] The polycarbonate resin according to [1], in which in Formula (1),at least one selected from Y¹ and Y² is a nitrogen atom.

[3] The polycarbonate resin according to [1] or [2], in which theconstitutional unit is a constitutional unit represented by Formula (2);

in Formula (2), R⁵ to R⁸ each independently represent a substituent; ato d are each independently 0 or more and represent an integer of themaximum number or less by which each ring is substitutable;

Ar¹¹ and Ar¹² each independently represent an aryl group including abenzene ring surrounded by a broken line or a heteroaryl group includinga benzene ring surrounded by a broken line as one of fused rings;

L¹ and L² each independently represent an alkylene group having 2 to 8carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, anarylene group having 6 to 20 carbon atoms, or a heteroarylene grouphaving 6 to 20 carbon atoms;

X¹ and X² each independently represent an oxygen atom or a sulfur atom;

n1 and n2 each independently represent an integer of 0 to 10; and

in a case where Ar¹¹ and Ar¹² are each independently an aromatic fusedring group including a benzene ring surrounded by a broken line, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or substitutedat a fused ring other than the benzene ring surrounded by a broken line.

[4] The polycarbonate resin according to any one of [1] to [3], furtherhaving a constitutional unit represented by Formula (11),

in Formula (11), R¹¹ is a group including at least one selected from analkylene group having 2 to 8 carbon atoms, a cycloalkylene group having5 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, anda heteroarylene group having 6 to 40 carbon atoms.

[5] The polycarbonate resin according to [4], in which R¹¹ in theconstitutional unit represented by Formula (11) includes a grouprepresented by Structure (12) or (13);

in Structures (12) and (13), * represents a linking site in a main chainof the constitutional unit represented by Formula (11).

[6] The polycarbonate resin according to [4] or [5], in which a totalamount of the constitutional unit represented by Formula (1) and theconstitutional unit represented by Formula (11) is 90 mol % or more withrespect to the entire constitutional unit of the polycarbonate resin,and in which a molar ratio of the constitutional unit represented byFormula (1) and the constitutional unit represented by Formula (11) is40:60 to 90:10.

[7] A molded article of the polycarbonate resin according to any one of[1] to [6].

[8] An optical member comprising the molded article according to [7].

[9] A lens comprising the molded article according to [7].

According to the present invention, it is possible to obtain a moldedarticle having a sufficiently low Abbe number and a high abnormaldispersibility. The molded article molded from a resin according to thepresent invention has the above characteristics, and thus is preferablyused in an optical member, a lens, or the like.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention is specifically described. Thefollowing description of components may be made based on arepresentative embodiment or a specific example, but the presentinvention is not limited to the embodiment. In the presentspecification, the numerical range expressed by using “to” means a rangeincluding numerical values described before and after “to” as a lowerlimit value and an upper limit value.

In the present specification, with respect to a group (atomic group), ina case where substitution or unsubstitution is not described, the groupincludes both of a group having a substituent and a group not having asubstituent. For example, an “alkyl group” includes not only an alkylgroup not having a substituent (unsubstituted alkyl group) but also analkyl group having a substituent (substituted alkyl group).

(Polycarbonate Resin)

The present invention relates to a polycarbonate resin including aconstitutional unit represented by Formula (1).

In Formula (1), Y¹ and Y² are each independently an oxygen atom, asulfur atom, a nitrogen atom, or a carbon atom, and at least one Y¹ orY² is an oxygen atom, a sulfur atom, or a nitrogen atom. Z is an atomicgroup for forming a 5- to 7-membered ring together with Y¹—C═C—Y², andrepresents an atomic group including at least one selected from a carbonatom and a heteroatom.

R⁵ to R⁸ each independently represent a substituent.

a to d are each independently 0 or more, and represent an integer of themaximum number or less by which each ring is substitutable.

Ar¹¹ and Ar¹² each independently represent an aryl group including abenzene ring surrounded by a broken line or a heteroaryl group includinga benzene ring surrounded by a broken line as one of fused rings.

L¹ and L² each independently represent an alkylene group having 2 to 8carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, anarylene group having 6 to 20 carbon atoms, or a heteroarylene grouphaving 6 to 20 carbon atoms.

X¹ and X² each independently represent an oxygen atom or a sulfur atom.

n1 and n2 each independently represent an integer of 0 to 10.

In a case where Ar¹¹ and Ar¹² are each independently an aromatic fusedring group including a benzene ring surrounded by a broken line, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or may besubstituted at a fused ring other than the benzene ring surrounded by abroken line.

In a case where a is an integer of 2 to 4, a plurality of R⁵'s may beidentical to or different from each other, and a plurality of R⁵'s maybe bonded to each other to form a ring.

In a case where b is an integer of 2 to 4, a plurality of R⁶'s may beidentical to or different from each other, and a plurality of R⁶'s maybe bonded to each other to form a ring.

In a case where c is an integer of 2 to 4, a plurality of R⁷'s may beidentical to or different from each other, and a plurality of R⁷'s maybe bonded to each other to form a ring.

In a case where d is an integer of 2 or more, a plurality of R⁸'s may beidentical to or different from each other, and a plurality of R⁸'s maybe bonded to each other to form a ring.

Since the polycarbonate resin of the present invention is apolycarbonate resin including the above constitutional unit, it ispossible to form a molded article having a sufficiently low Abbe numberand a high abnormal dispersibility. The polycarbonate resin of thepresent invention may form a molded article having a sufficiently highrefractive index.

In a case where a molded article is molded from a polycarbonate resin inthe present invention, the moldability thereof is satisfactory, and thegeneration of the optical strain in the molded article may besuppressed. Since the polycarbonate resin of the present invention is aresin including the constitutional unit, solvent solubility is high andfluidity is excellent.

In this manner, the molded article molded from the polycarbonate resinof the present invention also has excellent optical properties, and thushas a high quality as an optical member. Since the fluidity of the resinis excellent, moldability is satisfactory.

In Formula (1), Y¹ and Y² are each independently an oxygen atom, asulfur atom, a nitrogen atom, or a carbon atom, and at least one of Y¹or Y² is an oxygen atom, a sulfur atom, or a nitrogen atom. It ispreferable that Y¹ and Y² are each independently a nitrogen atom or acarbon atom, and it is preferable that at least one selected from Y¹ andY² is a nitrogen atom. It is more preferable that both of Y¹ and Y² arenitrogen atoms.

In Formula (1), Z is an atomic group that forms a 5- to 7-membered ringtogether with Y¹—C═C—Y² and represents an atomic group including atleast one selected from a carbon atom and a heteroatom. Z is preferablyan atomic group for forming a 5 or 6-membered ring together withY¹—C═C—Y² and is more preferably an atomic group for forming a6-membered ring. Z may be an atomic group including at least oneselected from a carbon atom and a heteroatom, is preferably an atomicgroup including a carbon atom, and more preferably an atomic groupincluding only a carbon atom.

In Formula (1), R⁵ to R⁸ each independently represent a substituent. Thesubstituents represented by R⁵ to R⁸ are not particularly limited, andexamples thereof include a halogen atom, a halogenated alkyl group, analkyl group, an alkenyl group, an acyl group, a hydroxyl group, ahydroxyalkyl group, an alkoxy group, an aryl group, a heteroaryl group,an alicyclic group, and a cyano group. The substituent represented by R⁵to R⁸ is preferably a halogen atom, an alkyl group, an alkoxy group, anaryl group, or a cyano group, more preferably a halogen atom, an alkylgroup having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbonatoms, a phenyl group, or a cyano group, and particularly preferably ahalogen atom, a methyl group, a methoxy group, a phenyl group, or acyano group.

The substituents represented by R⁵ to R⁷ are each independently andpreferably an alkyl group, an alkoxy group, or an aryl group, morepreferably an alkyl group having 1 to 5 carbon atoms, an alkoxy grouphaving 1 to 5 carbon atoms, or a phenyl group, and particularlypreferably a methyl group or a methoxy group.

R⁸ is preferably an alkyl group, a silyl group, an alkoxy group, or anaryl group, more preferably an alkyl group having 1 to 5 carbon atoms, asilyl group, an alkoxy group having 1 to 5 carbon atoms, or a phenylgroup, and even more preferably a methyl group, a silyl group, or amethoxy group. The plurality of R⁸'s are more preferably groups thatform a fused ring with a substituted ring.

In Formula (1), a to d are each independently 0 or more and represent aninteger of the maximum number or less by which each ring issubstitutable. a to c are each independently and preferably an integerof 0 to 4, more preferably an integer of 0 to 3, even more preferably aninteger of 0 to 2, still even more preferably 0 or 1, and particularlypreferably 0. d is preferably an integer of 0 to 3 and more preferablyan integer of 0 to 2.

In a case where a is an integer of 2 to 4, a plurality of R⁵'s may beidentical to or different from each other. The plurality of R⁵'s may bebonded to each other to form a ring, but it is preferable that theplurality of R⁵'s are not bonded to each other to form a ring.

In a case where b is an integer of 2 to 4, a plurality of R⁶'s may beidentical to or different from each other. The plurality of R⁶'s may bebonded to each other to form a ring, but it is preferable that theplurality of R⁶'s are not bonded to each other to form a ring.

In a case where c is an integer of 2 to 4, a plurality of R⁷'s may beidentical to or different from each other. The plurality of R⁷'s may bebonded to each other to form a ring, but it is preferable that theplurality of R⁷'s are not bonded to each other to form a ring.

In a case where d is an integer of 2 or more, a plurality of R⁸'s may beidentical to or different from each other, and a plurality of R⁸'s maybe bonded to each other to form a ring. Among these, in a case where dis an integer of 2 or more, the plurality of R⁸'s are preferably groupsthat are bonded to each other to form a fused ring together with asubstituted ring. The fused ring may further have a substituent, and inthis case, as the substituent, the substituents exemplified as R⁸ may beexemplified as preferable substituents.

In a case where the plurality of R⁸'s are groups that are bonded to eachother to form a fused ring together with a substituted ring, the numberof rings for forming a fused ring is preferably 4 or less, morepreferably 3 or less, and even more preferably 2. In a case where thenumber of rings for forming a fused ring is in the above range, thecoloration of the polycarbonate resin including the constitutional unitis easily suppressed.

In Formula (1), Ar¹¹ and Ar¹² each independently represent an aryl groupincluding a benzene ring surrounded by a broken line or a heteroarylgroup including a benzene ring surrounded by a broken line as one offused rings. Among these, Ar¹¹ and Ar¹² are each independently andpreferably an aryl group including a benzene ring surrounded by a brokenline. In a case of an aryl group including a benzene ring surrounded bya broken line represented by Ar¹¹ and Ar¹², the aryl group is preferablyan aryl group having 6 to 18 carbon atoms, more preferably an aryl grouphaving 6 to 14 carbon atoms, and particularly preferably an aryl grouphaving 6 to 10 carbon atoms. In a case of a heteroaryl group including abenzene ring surrounded by a broken line as one of fused ringsrepresented by Ar¹¹ and Ar¹², the heteroaryl group is preferably aheteroaryl group having 9 to 14 ring members and more preferably aheteroaryl group having 9 or 10 ring members. Examples of the heteroatomforming the heteroaryl group that may have a substituent represented byAr¹¹ and Ar¹² include a nitrogen atom, an oxygen atom, and a sulfuratom.

Ar¹¹ and Ar¹² may be each independently an aryl group only including abenzene ring surrounded by a broken line and may be an aromatic fusedring group including a benzene ring surrounded by a broken line as oneof fused rings. In the present specification, the fused ring of thearomatic fused ring group has aromaticity as the entire fused ring.

In Formula (1), L¹ and L² are each independently an alkylene grouphaving 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbonatoms, an arylene group having 6 to 20 carbon atoms, or a heteroarylenegroup having 6 to 20 carbon atoms. L¹ and L² are each independently andpreferably an alkylene group having 2 to 8 carbon atoms and morepreferably an alkylene group having 2 to 4 carbon atoms.

In Formula (1), X¹ and X² each independently represent an oxygen atom ora sulfur atom. Among these, X¹ and X² each are preferably an oxygenatom.

In Formula (1), n1 and n2 may be each independently an integer of 0 to10, is preferably an integer of 0 to 4, more preferably an integer of 0to 2, and even more preferably 0 or 1.

In Formula (1), in a case where Ar¹¹ and Ar¹² are each independently anaromatic fused ring group including a benzene ring surrounded by abroken line as one of fused rings, R⁵, R⁶, —X¹-[L¹-O]_(n1)—, and—X²-[L²-O]_(n2)— may be each independently substituted at a benzene ringsurrounded by a broken line or substituted at a fused ring other thanthe benzene ring surrounded by a broken line.

The constitutional unit is preferably a constitutional unit representedby Formula (2).

In Formula (2), R⁵ to R⁸ each independently represent a substituent. ato d are each independently 0 or more and represent an integer of themaximum number or less by which each ring is substitutable.

Ar¹¹ and Ar¹² each independently represent an aryl group including abenzene ring surrounded by a broken line or a heteroaryl group includinga benzene ring surrounded by a broken line as one of fused rings.

L¹ and L² each independently represent an alkylene group having 2 to 8carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, anarylene group having 6 to 20 carbon atoms, or a heteroarylene grouphaving 6 to 20 carbon atoms.

X¹ and X² each independently represent an oxygen atom or a sulfur atom.

n1 and n2 each independently represent an integer of 0 to 10.

In a case where Ar¹¹ and Ar¹² are each independently an aromatic fusedring group including a benzene ring surrounded by a broken line, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or substitutedat a fused ring other than the benzene ring surrounded by a broken line.

In a case where a is an integer of 2 to 4, a plurality of R⁵'s may beidentical to or different from each other, and a plurality of R⁵'s maybe bonded to each other to form a ring.

In a case where b is an integer of 2 to 4, a plurality of R⁶'s may beidentical to or different from each other, and a plurality of R⁶'s maybe bonded to each other to form a ring.

In a case where c is an integer of 2 to 4, a plurality of R⁷'s may beidentical to or different from each other, and a plurality of R⁷'s maybe linked to each other to form a ring.

In a case where d is an integer of 2 or more, a plurality of R⁸'s may beidentical to or different from each other, and a plurality of R⁸'s maybe bonded to each other to form a ring.

The preferable ranges of R⁵ to R⁸ in Formula (2) are the same as thepreferable ranges of R⁵ to R⁸ in Formula (1).

The preferable ranges of Ar¹¹ and Ar¹² in Formula (2) are the same asthe preferable ranges of Ar¹¹ and Ar¹² in Formula (1).

The preferable ranges of L¹ and L² in Formula (2) are the same as thepreferable ranges of L¹ and L² in Formula (1).

The preferable ranges of X¹ and X² in Formula (2) are the same as thepreferable ranges of X¹ and X² in Formula (1).

The preferable ranges of a to c in Formula (2) are the same as thepreferable ranges of a to c in Formula (1).

The preferable ranges of n1 and n2 in Formula (2) are the same as thepreferable ranges of n1 and n2 in Formula (1).

d in Formula (2) may be an integer of 0 to 2. In a case where d is aninteger of 2, the plurality of R⁸'s may be identical to or differentfrom each other, and it is preferable that the plurality of R⁸'s arebonded to each other to form a ring. The fused ring may further have asubstituent, and in this case, examples of the substituent includesubstituents exemplified as R⁸ as preferable substituents.

Hereinafter, specific examples of the constitutional unit represented byFormula (1) are listed, but the present invention is not limited to thefollowing constitutional units.

A method of obtaining the constitutional unit represented by Formula (1)is not particularly limited, and a compound to be a precursor may beobtained in a commercial way or may be manufactured by synthesis. In acase where the compound to be a precursor is manufactured by synthesis,the compound may be synthesized in a well-known method or a methoddescribed in the example.

The polycarbonate resin of the present invention is preferably apolycarbonate resin further including a constitutional unit representedby Formula (11). In a case where the polycarbonate resin furthercontains a constitutional unit represented by Formula (11), themoldability in a case where the polycarbonate resin is molded may befurther increased, and thus the generation of the optical strain in themolded article may be effectively suppressed.

In Formula (11), R¹¹ is a group including at least one selected from analkylene group having 2 to 8 carbon atoms, a cycloalkylene group having5 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, anda heteroarylene group having 6 to 40 carbon atoms.

The alkylene group, the cycloalkylene group, the arylene group, and theheteroarylene group described above preferably have a substituent, andthe carbon atoms in the alkylene group and the cycloalkylene group maybe substituted with an O atom or a S atom.

R¹¹ may be a linking group including the above groups, may be a linkinggroup including only the above groups, or may be a linking group havinga structure obtained by combining two or more of the above groups. R¹¹may be a linking group containing at least one selected from an etherbond and a thioether bond between the above groups. In this case, atleast one selected from an ether bond and a thioether bond may bepresent between the same kinds of groups or may be present betweendifferent kinds of groups.

R¹¹ is a group not including —O—C(═O)—O—.

Among these, R¹¹ is preferably a group including at least one selectedfrom an alkylene group having 2 to 8 carbon atoms and an arylene grouphaving 6 to 40 carbon atoms and more preferably an alkylene group having2 to 8 carbon atoms or a group having a structure obtained by combiningan alkylene group having 2 to 8 carbon atoms and an arylene group having6 to 40 carbon atoms.

Hereinafter, specific examples of R¹¹ of the constitutional unitrepresented by Formula (11) are listed, but the structure of R¹¹ is notlimited to the following structure. In the following specificexamples, * represents a linking site in a main chain of theconstitutional unit represented by Formula (11).

Among these, R¹¹ in the constitutional unit represented by Formula (11)is preferably a group represented by Structure (12) or (13).

In Structures (12) and (13), * represents a linking site in a main chainof the constitutional unit represented by Formula (11).

A method of obtaining the constitutional unit represented by Formula(11) is not particularly limited, and the compound to be a precursor maybe obtained in a commercial way or may be manufactured by synthesis. Ina case where the compound to be a precursor is manufactured bysynthesis, the compound may be synthesized in a well-known method or amethod described in the example.

According to the present invention, the content of the constitutionalunit represented by Formula (1) is preferably 40 mol % or more, morepreferably 50 mol % or more, and even more preferably 70 mol % or morewith respect to the entire constitutional unit of the polycarbonateresin.

In a case where the polycarbonate resin includes the constitutional unitrepresented by Formula (11), the content of the constitutional unitrepresented by Formula (11) is preferably 60 mol % or less, morepreferably 50 mol % or less, even more preferably 45 mol % or less, andparticularly preferably 40 mol % or less with respect to the entireconstitutional unit of the polycarbonate resin. In a case where theproportion of the constitutional unit included in the polycarbonateresin is set to be in the above range, the Abbe number of the moldedarticle may be more effectively reduced.

In a case where the polycarbonate resin includes the constitutional unitrepresented by Formula (11), the total amount of the constitutional unitrepresented by Formula (1) and the constitutional unit represented byFormula (11) is even more preferably 90 mol % or more with respect tothe entire constitutional unit of the polycarbonate resin. Among these,the molar ratio of the constitutional unit represented by Formula (1)and the constitutional unit represented by Formula (11) is preferably40:60 to 90:10. The proportion of the constitutional unit in thepolycarbonate resin is in the above range, the molded article may have alow Abbe number, and the durability of the molded article may be furtherincreased.

Hereinafter, the constitutional units included in the polycarbonateresin of the present invention and the molar ratio of the constitutionalunits are exemplified, but the configuration of the polycarbonate resinis not limited as below.

TABLE 1 Polycarbonate Constitutional Constitutional resin unit (a) mol %unit (b) mol % P-1 (a-1) 100 P-2 (a-8) 100 P-3 (a-6) 100 P-4 (a-2) 100P-5 (a-11) 100 P-6 (a-1) 70 (b-7) 30 P-7 (a-1) 70 (b-19) 30 P-8 (a-1) 70(b-17) 30 P-9 (a-2) 80 (b-5) 20 P-10 (a-2) 60 (b-6) 40 P-11 (a-2) 70(b-7) 30 P-12 (a-2) 70 (b-9) 30 P-13 (a-2) 70 (b-16) 30 P-14 (a-2) 70(b-17) 30 P-15 (a-2) 70 (b-18) 30 P-16 (a-2) 70 (b-19) 30 P-17 (a-2) 70(b-22) 30 P-18 (a-1) 50 (b-7) 50 P-19 (a-1) 20 (b-7) 80 P-20 (a-8) 20(b-7) 80 P-21 (a-5) 20 (b-7) 80 P-22 (a-6) 20 (b-7) 80 P-23 (a-7) 20(b-7) 80 P-24 (a-10) 20 (b-7) 80 P-25 (a-12) 20 (b-7) 80 P-26 (a-2) 20(b-7) 80 P-27 (a-11) 20 (b-7) 80 P-28 (a-1) 60 (b-22) 40 P-29 (a-8) 60(b-22) 40 P-30 (a-6) 50 (b-22) 50 P-31 (a-2) 90 (b-22) 10 P-32 (a-1) 70(b-1) 30 P-33 (a-8) 70 (b-1) 30 P-34 (a-6) 70 (b-1) 30 P-35 (a-2) 90(b-1) 10 P-36 (a-11) 90 (b-1) 10

A viscosity average molecular weight of the polycarbonate resin of thepresent invention is preferably 5,000 or more, more preferably 10,000 ormore, and even more preferably 13,000 or more. The viscosity averagemolecular weight of the polycarbonate resin is preferably 100,000 orless and more preferably 50,000 or less.

Here, the viscosity average molecular weight of the polycarbonate resinis calculated by dissolving the polycarbonate resin in 100 ml ofmethylene chloride to obtain a solution and using the following equationfrom specific viscosity (η_(sp)) of the solution at 20° C.

η_(sp) /c=[η]+0.45×[η]² c (here, [η] is intrinsic viscosity)

[η]=1.23×10⁻⁴ M^(0.83)

c=0.7

(Polymerization Method of Polycarbonate Resin)

The polycarbonate resin of the present invention may be polymerized byusing well-known reaction means. Examples thereof include (a) a fusingmethod performed by reacting phosgene with at least one selected fromdihydric phenol and a derivative of dihydric phenol or (b) a method ofperforming transesterification on at least one selected from dihydricphenol and a derivative of dihydric phenol by using a carbonateprecursor material such as carbonic acid diester. Hereinafter, the atleast one selected from dihydric phenol and a derivative of dihydricphenol is simply referred to as dihydric phenol in some cases.

As the dihydric phenol, the compound that may become the constitutionalunit represented by Formula (1) is preferably used. As the derivative ofdihydric phenol, a chlorocarbonic acid compound or the like that maybecome the constitutional unit represented by Formula (1) is preferablyused.

In a case where the constitutional unit represented by Formula (11) isincluded as the constitutional unit of the polycarbonate resin, as thedihydric phenol or the derivative of the dihydric phenol, a compoundthat may become the constitutional unit represented by Formula (11) orthe chlorocarbonic acid compound that may become the constitutional unitrepresented by Formula (11) may be used.

In a case where the polycarbonate resin is polymerized, a catalyst, aterminating agent, an antioxidant of dihydric phenol, a heat stabilizer,or the like may be used, if necessary.

The reaction using (a) the fusing method for reacting phosgene is thereaction between dihydric phenol and phosgene and is performed in thepresence of an acid binder and an organic solvent. As the acid binder,for example, alkali metal hydroxide such as sodium hydroxide orpotassium hydroxide or an amine compound such as pyridine is used. Asthe organic solvent, for example, halogenated hydrocarbon such asmethylene chloride and chlorobenzene is used. In order to promote thereaction, for example, a catalyst such as tertiary amine such astriethylamine, tetra-n-butylammonium bromide, ortetra-n-butylphosphonium bromide, a quaternary ammonium compound, and aquaternary phosphonium compound may be used. In this case, it ispreferable that the reaction temperature is usually at 0° C. to 40° C.,the reaction time is about 10 minutes to 5 hours, and the pH during thereaction is maintained to 9 or more.

The reaction using (b) the transesterification method istransesterification reaction between dihydric phenol and carbonateester, and is performed by a method of mixing dihydric phenol andcarbonate ester while heating in the presence of an inert gas anddistilling off generated alcohol or phenol or the like. The reactiontemperature varies depending on the boiling point of the generatedalcohol or phenol but is generally in the range of 120° C. to 350° C.During the latter stage of the reaction, the system is depressurized toabout 1.3×10³ to 1.3×10 Pa such that the distillation of the generatedalcohol or phenol is easily performed. The reaction time is generallyabout 1 to 4 hours.

Examples of the carbonate ester include ester such as an aryl grouphaving 6 to 10 carbon atoms which may have a substituent, an aralkylgroup, or an alkyl group having 1 to 4 carbon atoms. Specific examplesthereof include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate,and among these, diphenyl carbonate is preferable.

In the reaction using (b) the transesterification method, in order toincrease the polymerization rate, a polymerization catalyst may be used,and as the polymerization catalyst, a catalyst used for generalesterification reaction or transesterification reaction such as analkali metal compound such as sodium hydroxide, potassium hydroxide,sodium salt of dihydric phenol, and potassium salt, an alkali earthmetal compound such as calcium hydroxide, barium hydroxide, andmagnesium hydroxide, a nitrogen-containing basic compound such astetramethylammonium hydroxide, tetraethylammonium hydroxide,trimethylamine, and triethylamine, and alkoxides of alkali metal andalkaline earth metal, organic acid salts of alkali metal and alkaliearth metal, zinc compounds, boron compounds, aluminum compounds,silicon compounds, germanium compounds, organotin compounds, leadcompounds, osmium compounds, antimony compounds, manganese compounds,titanium compounds, and zirconium compounds may be used. The catalystsmay be used singly or two or more kinds thereof may be used incombination. The usage amount of the polymerization catalyst ispreferably 1×10⁻⁸ to 1×10⁻³ equivalent with respect to 1 mol of dihydricphenol of a raw material.

In the polymerization reaction, as the polycarbonate resin,monofunctional phenols that are generally used as a terminating agentmay be used. For example, in the case of the reaction using phosgene,since monofunctional phenols are used as a terminating agent in order toadjust the molecular weight, and the obtained polycarbonate resin issealed by a group of which the terminal is based on monofunctionalphenols, heat stability is excellent.

(Method of Manufacturing Molded Article)

A molded article may be manufactured from a resin composition includingthe polycarbonate resin. Examples of the method of molding the moldedarticle include hot pressure molding, and, for example, compressionmolding, injection molding, extrusion molding, blow molding, embossmolding, and the like may be employed. Among these, in a case of moldingthe molded article of the present invention, it is preferable to employinjection molding.

It is preferable to add an antioxidant such as triphenyl phosphite ortris(2,4-di-tert-butylphenyl) phosphite to a resin composition includinga polycarbonate resin. The addition amount of the antioxidant ispreferably 0.00001 to 0.0001 mass % with respect to the total mass ofthe resin composition.

It is preferable that, as an antistatic agent, an anionic surfactant, acationic surfactant, a nonionic surfactant, an amphoteric surfactant, asurfactant mixture, or the like is added to the resin compositionincluding the polycarbonate resin. Examples of the antistatic agentinclude monoglyceride stearate. The addition amount of the antistaticagent is preferably 0.01 to 0.1 mass % with respect to the total mass ofthe resin composition.

Before injection molding is performed, a resin composition including apolycarbonate resin may be pelletized. By pelletizing the polycarbonateresin, the handleability of the resin in a case of injection molding maybe enhanced. In a case of pelletizing the resin composition, forexample, a vent type single screw extruder or the like may be used.

In the case of injection molding, an injection molding machine(including an injection compression molding machine) is used. In theinjection molding machine, a polycarbonate molten resin is collected onthe tip of a cylinder, and then the polycarbonate molten resin isinjected into a die and molded. As the injection molding machine, agenerally used injection molding machine may be used. It is preferablethat the cylinder is formed of a material having low adherence to thepolycarbonate resin and exhibiting corrosion resistance and wearresistance. As an injection molding machine, for example, Micro-1manufactured by Meiho Co., Ltd. can be exemplified.

The cylinder temperature in a case of injection molding is preferably200° C. to 450° C. and more preferably 250° C. to 390° C. Thetemperature of the die is preferably 50° C. to 300° C. and morepreferably 100° C. to 250° C.

It is preferable that the environment in which the molding process iscarried out is as clean as possible. It is also preferable tosufficiently dry a material to be provided in the molding so as toremove moisture or to perform molding without retention which causesdecomposition of the molten resin.

(Molded Article)

The present invention relates to a molded article of the abovepolycarbonate resin. In the molded article of the polycarbonate resin,in addition to the polycarbonate resin, an additive such as anantioxidant, an antistatic agent, or a heat stabilizer may be included.In a case where the molded article includes various additives, thecontent of the additive is preferably 5 mass % or less with respect tothe total mass of the molded article.

As described below, the molded article of the present invention ispreferably used in an application of an optical member, and among these,it is preferable to be used as a lens. In this point of view, it ispreferable that the refractive index of the molded article is high. Inthe molded article of the present invention, a refractive index nD at awavelength of 589 nm is preferably 1.45 or more, more preferably 1.58 ormore, even more preferably 1.60 or more, and particularly preferably1.64 or more.

The molded article of the present invention preferably has a low Abbenumber, in view of decreasing the chromatic aberration in a case ofbeing used as a lens or the like among applications as an opticalmember. In the molded article of the present invention, the Abbe numberis preferably 25 or less, more preferably 24 or less, even morepreferably 22 or less, still even more preferably 21 or less, andparticularly preferably 20 or less. The Abbe number of the moldedarticle of the present invention is preferably 13 to or more.

In the present specification, an Abbe refractometer (manufactured byKalnew Optical Industrial Co., Ltd.) is used, the refractive indexes nD,nF, and nC at wavelengths of 589 nm, 486 nm, and 656 nm are measured,and the Abbe number (vD) is calculated by the following equation.

vD=(nD−1)/(nF−nC)

Here, nD represents a refractive index at a wavelength of 589 nm, nFrepresents a refractive index at a wavelength of 486 nm, and nCrepresents a refractive index at a wavelength of 656 nm.

With respect to the molded article of the present invention, it ispreferable that abnormal dispersibility is high. The abnormaldispersibility of the molded article of the present invention ispreferably more than 0.50, more preferably 0.55 or more, and even morepreferably 0.60 or more.

In the present specification, an Abbe refractometer (manufactured byKalnew Optical Industrial Co., Ltd.) is used, the refractive indexes nD,nF, nC, and ng at a wavelength of 589 nm, 486 nm, 656 nm, and 435.8 nmare measured, and the abnormal dispersibility (θgF) is calculated by thefollowing equation.

θgF=(ng−nF)/(nF−nC)

Here, nD represents a refractive index at a wavelength of 589 nm, nFrepresents a refractive index at a wavelength of 486 nm, nC represents arefractive index at a wavelength of 656 nm, and ng represents arefractive index at a wavelength of 435.8 nm.

The maximum thickness of the molded article of the present invention ispreferably 0.1 to 10 mm. The maximum thickness is more preferably 0.1 to5 mm and particularly preferably 0.15 to 3 mm. The maximum diameter ofthe molded article of the present invention is preferably 1 to 1,000 mm.The maximum diameter is more preferably 2 to 200 mm and particularlypreferably 2.5 to 100 mm. The molded article of this size isparticularly useful as the application as an optical member having ahigh refractive index.

(Optical Member)

The present invention also relates to an optical member including theabove molded article. The molded article of the present invention is amolded article having excellent optical properties, and thus ispreferably used in an optical member. The type of the optical member ofthe present invention is not particularly limited, and the opticalmember may be suitably used as an optical member using the excellentoptical properties of the molded article, particularly, an opticalmember (so-called passive optical member) that transmits light. Examplesof the optical functional device having such an optical member includevarious display devices (liquid crystal display, plasma display, and thelike), various projector devices (overhead projector (OHP), liquidcrystal projector, and the like), an optical fiber communication device(optical waveguide, optical amplifier, and the like), and an imagingdevice such as cameras and video.

Examples of the passive optical member used in the optical functionaldevice include a lens, a prism, a prism sheet, a panel (plate-likemolded article), a film, an optical waveguide (having a film shape, afiber shape, or the like), an optical disc, and a sealing agent of alight emitting diode (LED). Such a passive optical member may beprovided with any coating layer, if necessary, for example, a protectivelayer for preventing mechanical damage of the coated surface such asfriction or abrasion, a light absorbing layer for absorbing light havingundesirable wavelengths causing deterioration of inorganic particles, asubstrate, or the like, a permeation shielding layer for suppressing orpreventing permeation of reactive low molecular weight molecules such asmoisture and oxygen gas, an antiglare layer, an antireflection layer, alayer of a low refractive index, and any additional functional layers.Specific examples of the any coating layer include a transparentconductive film or a gas barrier film including an inorganic oxidecoating layer, and a gas barrier film or a hard coat film including anorganic substance coating layer. As a coating method, known coatingmethods such as a vacuum deposition method, a chemical vapor deposition(CVD) method, a sputtering method, a dip coating method, and a spincoating method may be used.

Application Example

The optical member using the molded article of the present invention ispreferably used particularly in a lens substrate. The lens substratemanufactured by using the polycarbonate resin of the present inventionhas a low Abbe number, preferably further has a high refractive index,light transmittance, and light weight, and has excellent opticalproperties.

In the present specification, a “lens substrate” means a single memberthat may exhibit a lens function. A film or a member may be provided onthe surface or the periphery of the lens substrate according to the useenvironment and application of the lens. For example, a protective film,an antireflection film, a hard coat film, and the like may be formed onthe surface of the lens substrate. A composite lens obtained bylaminating glass lens substrates or plastic lens substrates may beprovided. The periphery of the lens substrate may be fitted and fixedinto the substrate holding frame or the like. However, these films,frames, and the like are members to be added to the lens substrate andare distinguished from the lens substrate in the present specification.

In a case where the lens substrate is used as a lens, the lens substratemay be used as a lens alone, or the film, the frame, other lenssubstrates, and the like may be added to the lens substrate to be usedas a lens. The types and the shapes of the lens using the lens substrateare not particularly limited.

The lens substrate has a low Abbe number, and thus may be preferablyused in a chromatic aberration correcting lens, and the chromaticaberration correcting lens, for example, is preferably used for an imagepickup lens of mobile phones, digital cameras, and the like, an imaginglens of televisions, video cameras, and the like, an in-vehicle lens,and an endoscope lens.

Examples

Hereinafter, characteristics of the present invention are morespecifically described with reference to the examples and comparativeexamples. A material, a usage amount, a proportion, a treatment detail,a treatment order, and the like provided in the following examples canbe suitably changed without departing from the gist of the presentinvention. Accordingly, the scope of the present invention should not beconstrued in a limited manner by the following specific examples.

Example 1

<Synthesis of A-1>

50 mL of ethanol and 10 mL of acetic acid were added to 21.6 g (0.2 mol)of o-phenylenediamine and 35.6 g (0.2 mol) of ninhydrin, and reactionwas performed at 70° C. for three hours. After the reaction solution wascooled to room temperature, the precipitated crystals were collected byfiltration, washed with ethanol, and dried so as to obtain 40.9 g (0.18mol) of Compound (A-1-1).

20 g (86 mmol) of Compound (A-1-1) and 41.5 g (340 mmol) of2,6-dimethylphenol were dissolved in 30 mL of methanesulfonic acid. Thereaction solution was warmed and maintained at 100° C., and 0.3 mL of3-mercaptopropionic acid was added dropwise. After stirring wasperformed for three hours, 70 mL of toluene was added dropwise to thereaction solution and, the mixture was stirring for 30 minutes, and 140mL of toluene was further added dropwise. The reaction solution wasreturned to room temperature, and the precipitated crystals werecollected by filtration so as to obtain 33 g (72 mmol) of Compound(A-1). ¹H-NMR data of Compound (A-1) was as follows.

¹H-NMR (300 MHz, DMSO-d6): δ2.10 ppm (s, 12H), 6.70 ppm (bs, 2H), 6.80ppm (s, 4H), 7.55-7.70 ppm (m, 3H), 7.75-7.90 ppm (m, 2H), 8.00-8.10 ppm(d, 1H), 8.12-8.22 ppm (m, 2H)

<Synthesis of P-1>

103.05 g of a 25% sodium hydroxide aqueous solution and 309.15 g of ionexchange water were introduced to a reactor equipped with a stirrer, athermometer, and a reflux condenser, 98.3 g (214.4 mmol) of Compound(A-1) was dissolved therein, and a small amount of hydrosulfite wasadded. Subsequently, 20.64 g of ion exchange water, 14.17 g of a 48%sodium hydroxide aqueous solution, and 237.23 g of methylene chloridewere added, and 27.63 g (279 mmol) of phosgene was blown at 20° C. overabout 60 minutes. A solution obtained by dissolving 1.13 g ofp-tert-butylphenol in 3 g of methylene chloride and 17.17 g of a 25%sodium hydroxide aqueous solution were added to this solution foremulsification, then 0.12 g of triethylamine was added, and stirring wasperformed for about three hours at 30° C., so as to complete thereaction. After completion of the reaction, methylene chloride wasadded, the mixture was diluted and washed with water, then the organicphase was separated, and methylene chloride was evaporated to obtainPolycarbonate Resin (P-1) including (a-1) as a constitutional unit.

Example 2

<Synthesis of A-8>

Compound (A-8) was synthesized in the same manner as in the synthesis ofCompound (A-1), except that 2,6-dimethylphenol was changed to phenol.¹H-NMR data was as follows.

¹H-NMR (300 MHz, DMSO (Dimethyl sulfoxide)-d6): δ 6.60-6.70 ppm (d, 4H),6.95-7.05 ppm (d, 4H), 7.55-7.70 ppm (m, 3H), 7.75-7.90 ppm (m, 2H),8.00-8.10 ppm (d, 1H), 8.12-8.22 ppm (m, 2H), 9.40 ppm (bs, 2H)

<Synthesis of P-2>

Polycarbonate Resin (P-2) including (a-8) as the constitutional unit wasobtained in the same manner as in <Synthesis of a-1> of Example 1 exceptthat (A-1) was changed to (A-8).

Example 3

<Synthesis of A-6>

Compound (A-6-1) was synthesized in a method disclosed in Journal ofHeterocyclic Chemistry, 1972, vol. 9, p. 1399.

60.9 g (647 mmol) of Compound (A-6-1) and 30.0 g (129 mmol) of phenolwere dissolved in 21 mL of toluene and 12 mL of methanesulfonic acid.The reaction solution was warmed and maintained at 100° C., and 0.48 mLof 3-mercaptopropionic acid was added dropwise. After being stirred forthree hours, 30 mL of toluene and 10 mL of dimethyl carbonate were addeddropwise to the reaction solution. The reaction solution was returned toroom temperature, and the precipitated crystals were collected byfiltration and were boiled and washed with 150 mL of toluene. 37 g (92mmol) of Compound (A-6) was obtained by filtration. ¹H-NMR data ofCompound (A-6) was as follows.

¹H-NMR (300 MHz, DMSO-d6): δ 4.00-4.10 ppm (m, 4H), 4.30-4.40 ppm (m,4H), 5.85-5.95 ppm (m, 1H), 6.15-6.25 ppm (m, 1H), 6.30-6.40 ppm (m,1H), 6.80-6.90 ppm (d, 4H), 7.00-7.10 ppm (d, 4H), 7.60-7.80 ppm (m,3H), 8.20 ppm (d, 1H)

<Synthesis of P-3>

Polycarbonate Resin (P-3) including (a-6) as the constitutional unit wasobtained in the same manner as in <Synthesis of P-1> of Example 1 exceptthat (A-1) was changed to (A-6).

Example 4

<Synthesis of A-2>

10.0 g (43 mmol) of Compound (A-1-1) and 30.0 g (215 mmol) of2-phenoxyethanol were dissolved in 15 ml of toluene and 12 ml ofmethanesulfonic acid. The reaction solution was warmed and maintained at120° C., and 0.16 mL of 3-mercaptopropionic acid was added dropwise. Thereaction solution was warmed and stirred for two hours at 150° C., andthen returned to room temperature. An upper layer of a two-phaseseparated organic layer was removed, 200 ml of ethyl acetate and waterwere added, and the mixture was stirred. Precipitated crystals werecollected by filtration and recrystallized in a mixed solvent of ethylacetate/hexane. 12 g (25 mmol) of Compound (A-2) was obtained byfiltration. ¹H-NMR data of Compound (A-2) was as follows.

¹H-NMR (300 MHz, DMSO-d6): δ3.66 ppm (tt, 4H), 3.92 ppm (t, 4H), 4.84ppm (t, 2H), 6.85 ppm (d, 4H), 7.11 ppm (t, 4H), 7.57-7.70 ppm (m, 3H),7.76-7.89 ppm (m, 2H), 8.04-8.10 ppm (m, 1H), 8.15-8.25 ppm (m, 2H)

<Synthesis of P-4>

Polycarbonate Resin (P-4) including (a-2) as the constitutional unit wasobtained in the same manner as in <Synthesis of P-1> of Example 1 exceptthat (A-1) was changed to (A-2).

Example 5

<Synthesis of A-11>

Compound (A-11) was synthesized in the same manner as in <Synthesis ofA-2> of Example 4 except that 2-phenoxyethanol was changed to3-mercaptophenylpropanol.

<Synthesis of P-5>

Polycarbonate Resin (P-5) including (a-11) as the constitutional unitwas obtained in the same manner as in <Synthesis of P-1> of Example 1,except that (A-1) was changed to (A-11).

Example 6

<Synthesis of P-6>

A sodium hydroxide aqueous solution and ion exchange water wereintroduced in a reactor equipped with a stirrer, a thermometer, a refluxcondenser, and Compound (A-1) and bisphenol A (BPA) as Compound (B-7)were dissolved in a molar ratio of 70:30, and a small amount ofhydrosulfite was added. Next, methylene chloride was added thereto, andphosgene was blown at 20° C. over about 60 minutes. p-tert-Butylphenolwas added and emulsified, triethylamine was added, stirring wasperformed at 30° C. for about three hours, and the reaction was ended.After completion of the reaction, the organic phase was separated, andmethylene chloride was evaporated, so as to obtain Polycarbonate Resin(Copolymer) (P-6) including (a-1) and (b-7) as constitutional units. Thecompositional ratio of the obtained copolymer was almost the same as themonomer introduction amount ratio.

Example 7

<Synthesis of P-7>

Polycarbonate Resin (Copolymer) (P-7) including (a-1) and (b-19) asconstitutional units was obtained in the same manner as in <Synthesis ofP-6> of Example 6, except that (B-7) was changed to (B-19).

Example 8

<Synthesis of P-8>

Polycarbonate Resin (Copolymer) (P-8) including (a-1) and (b-17) asconstitutional units was obtained in the same manner as in <Synthesis ofP-6> of Example 6, except that (B-7) was changed to (B-17).

Comparative Example 1

A polycarbonate resin was obtained in the same manner as in Example 1 ofJP2010-254806A. Structures of 9,9-bis(4-hydroxy-3-methylphenyl) fluorene(BCF (B-18)) and bis(4-hydroxy-3-methylphenyl) sulfide (HMPS (B-16))used in Example 1 of JP2010-254806A were as follows.

Comparative Example 2

A polycarbonate resin was obtained in the same manner as in ComparativeExample 3 of JP2010-254806A. Structures of bisphenol A (BPA (B-7)) and9,9-bis(4-hydroxyphenyl) fluorene (BPFL (B-17)) used in ComparativeExample 3 of JP2010-254806A were as follows.

Comparative Example 3

A polycarbonate resin was obtained in the same manner as in Example 2 ofJP401081B.

Comparative Example 4

A polycarbonate resin was obtained in the same manner as in ComparativeExample 2 except that bisphenol A (BPA) was not used.

(Manufacturing of Molded Article)

After the polycarbonate resins obtained in examples and comparativeexamples were dried at 100° C. for 24 hours, 0.0025 mass % oftris(2,4-di-tert-butylphenyl) phosphite and 0.05 mass % of monoglyceridestearate were added and uniformly mixed. Thereafter, the mixture waspelletized using a vent type single screw extruder and then injectionmolding was performed by using an injection molding machine (Micro-1,manufactured by Meiho Co., Ltd.). In the injection molding, a moldedarticle having a thickness of 1.0 mm, a width of 10 mm, and a length of20 mm was molded as a molded article for evaluation at a cylindertemperature of 360° C. and a die temperature of a temperature presentedin Table 2.

(Evaluation)

<Refractive Index, Abbe Number, and Abnormal Dispersibility>

The Refractive index, Abbe number (vD), and abnormal dispersibility(θgF) of the molded article for evaluation were measured by using theAbbe refractometer (manufactured by Kalnew Optical Industrial Co.,Ltd.).

vD=(nD−1)/(nF−nC)

θgF=(ng−nF)/(nF−nC)

Here, nD represents a refractive index at a wavelength of 589 nm, nFrepresents a refractive index at a wavelength of 486 nm, nC represents arefractive index at a wavelength of 656 nm, and ng represents arefractive index at a wavelength of 435.8 nm. In the column of therefractive index of Table 2, a refractive index at a wavelength of 589nm is presented.

With respect to the abnormal dispersibility (θgF), the evaluation isperformed in the following standard.

L: θgF≤0.500

M: 0.500<θgF≤0.600

H: 0.600≤θgF

<Moldability (Optical Strain)>

Evaluation was performed by sandwiching the molded article forevaluation between two polarizing plates and visually observing lightleakage from the back by using a direct nicole method.

A: There was no light leakage

B: Light leakage was slightly recognized

C: Light leakage was conspicuous

TABLE 2 A-1 A-8 A-6 A-2 A-11 B-7 B-19 B-17 mol % mol % mol % mol % mol %mol % mol % mol % Example 1 100 Example 2 100 Example 3 100 Example 4100 Example 5 100 Example 6 70 30 Example 7 70 30 Example 8 70 30Comparative Example 1 Comparative 30 70 Example 2 Comparative 30 Example3 Comparative 100 Example 4 Molding temperature Mold- (Die Refrac-ability B-18 B-16 temperature tive Abbe (Optical mol % mol % ° C.) indexnumber strain) θgF Example 1 200 1.67 17.2 B H Example 2 190 1.66 17.4 BH Example 3 200 1.67 17.1 B H Example 4 150 1.65 17.4 B H Example 5 1501.66 17.4 B H Example 6 170 1.64 20.8 A H Example 7 170 1.65 19.1 A HExample 8 200 1.66 19.0 A H Comparative 50 50 120 1.63 24.8 B M Example1 Comparative 190 1.62 25.4 B M Example 2 Comparative 70 190 1.62 25.8 BM Example 3 Comparative 200 1.63 24.2 B M Example 4

From Table 2, the molded article molded from the polycarbonate resin ofthe present invention has a low Abbe number and high abnormaldispersibility. In the molded article molded from the polycarbonateresin of the example, a refractive index was high and the generation ofan optical strain was small.

Meanwhile, in the molded articles molded from the polycarbonate resinsof the comparative examples, the Abbe number was high, and the abnormaldispersibility was reduced. There was a tendency in that the refractiveindexes of the molded articles molded from the polycarbonate resins ofthe comparative examples were low.

(Manufacturing of Composite Lens)

After the polycarbonate resin obtained in the example was dried for 24hours at 100° C., 0.0025 mass % of tris(2,4-di-tert-butylphenyl)phosphite and 0.05 mass % of monoglyceride stearate were added, anduniformly mixed. Thereafter, after pelletization using a vent typesingle screw extruder, the polycarbonate resin obtained in the examplewas injected into a molding die having a surface treated with chromiumnitride, a transparent glass lens (convex lens in which glassmaterial=BK7, diameter of 33 mm, center thickness of 3 mm, radius ofcurvature of the surface in contact with the resin=44.3 mm, and radiusof curvature of the surface not in contact with the resin=330.9 mm) wasapplied so as to cover all the surfaces on the side not in contact withthe molding die of the resin and was spread such that the diameter ofthe resin became 30 mm. Thereafter, after cooling, the molded articleand the die were separated so as to manufacture the composite lens.

What is claimed is:
 1. A polycarbonate resin having a constitutionalunit represented by Formula (1);

in Formula (1), Y¹ and Y² are each independently an oxygen atom, asulfur atom, a nitrogen atom, or a carbon atom, and at least one of Y¹or Y² is an oxygen atom, a sulfur atom, or a nitrogen atom; Z is anatomic group for forming a 5- to 7-membered ring together with Y¹—C═C—Y²and represents an atomic group including at least one selected from acarbon atom and a heteroatom; R⁵ to R⁸ each independently represent asubstituent; a to d are each independently 0 or more and represent aninteger of the maximum number or less by which each ring issubstitutable; Ar¹¹ and Ar¹² each independently represent an aryl groupincluding a benzene ring surrounded by a broken line or a heteroarylgroup including a benzene ring surrounded by a broken line as one offused rings; L¹ and L² each independently represent an alkylene grouphaving 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbonatoms, an arylene group having 6 to 20 carbon atoms, or a heteroarylenegroup having 6 to 20 carbon atoms; X¹ and X² each independentlyrepresent an oxygen atom or a sulfur atom; n1 and n2 each independentlyrepresent an integer of 0 to 10; and in a case where Ar¹¹ and Ar¹² areeach independently an aromatic fused ring group including a benzene ringsurrounded by a broken line as one of fused rings, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or substitutedat a fused ring other than the benzene ring surrounded by a broken line.2. The polycarbonate resin according to claim 1, wherein in Formula (1),at least one selected from Y¹ and Y² is a nitrogen atom.
 3. Thepolycarbonate resin according to claim 1, wherein the constitutionalunit is a constitutional unit represented by Formula (2);

in Formula (2), R⁵ to R⁸ each independently represent a substituent; ato d are each independently 0 or more and represent an integer of themaximum number or less by which each ring is substitutable; Ar¹¹ andAr¹² each independently represent an aryl group including a benzene ringsurrounded by a broken line or a heteroaryl group including a benzenering surrounded by a broken line as one of fused rings; L¹ and L² eachindependently represent an alkylene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 12 carbon atoms, an arylene group having6 to 20 carbon atoms, or a heteroarylene group having 6 to 20 carbonatoms; X¹ and X² each independently represent an oxygen atom or a sulfuratom; n1 and n2 each independently represent an integer of 0 to 10; andin a case where Ar¹¹ and Ar¹² are each independently an aromatic fusedring group including a benzene ring surrounded by a broken line, R⁵, R⁶,—X¹-[L¹-O]_(n1)—, and —X²-[L²-O]_(n2)— may be each independentlysubstituted at a benzene ring surrounded by a broken line or substitutedat a fused ring other than the benzene ring surrounded by a broken line.4. The polycarbonate resin according to claim 1, further having aconstitutional unit represented by Formula (11),

in Formula (11), R¹¹ is a group including at least one selected from analkylene group having 2 to 8 carbon atoms, a cycloalkylene group having5 to 12 carbon atoms, an arylene group having 6 to 40 carbon atoms, anda heteroarylene group having 6 to 40 carbon atoms.
 5. The polycarbonateresin according to claim 4, wherein R¹¹ in the constitutional unitrepresented by Formula (11) includes a group represented by Structure(12) or (13);

in Structures (12) and (13), * represents a linking site in a main chainof the constitutional unit represented by Formula (11).
 6. Thepolycarbonate resin according to claim 4, wherein a total amount of theconstitutional unit represented by Formula (1) and the constitutionalunit represented by Formula (11) is 90 mol % or more with respect to theentire constitutional unit of the polycarbonate resin, and wherein amolar ratio of the constitutional unit represented by Formula (1) andthe constitutional unit represented by Formula (11) is 40:60 to 90:10.7. A molded article of the polycarbonate resin according to claim
 1. 8.An optical member comprising the molded article according to claim
 7. 9.A lens comprising the molded article according to claim 7.